Method of manufacture of certain aryl acetic acids



NGY 11, l952 n.1.. LEHMANN Er A1.- 4 2,617,822'

METHOD OF MANUFACTURE OF CETAIN RYL ACETIC ACIDS l Filed sept. 2 6, 195o v -2 lsl-nina:'rswsH'Lffz'r .BY MAI* v M AfTQRMEYS.

Nav. 11, 1952 R. L. LEHMANN ET AL METHOD OF MANUFACTRE 0F' CERTAIN ARYL ACETIC ACIDS -Filed Sept. 26, .1950

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ATTORNEY-S.

Vacetic acid.

Patented Nov. 11, 1952 METHOD OF MANUFACTURE OF CERTAIN ARYL ACETIO 4ACIDS vRen Lon Lehmann, Paris,.and Josef'Lintnen La Garenne Colombes, France, -`assignors `to YBezel-Malena, Paris, France, a corporation of France Application September 26, 1950,SeralNo.-186;786 In France December 20, 1947 1 lift isknown `that vit is possible to preparefthe a-naphthylacetic acid through-a direct-reaction between the naphthalene and the monochlor- According to the `U. S. Patent 1,951,686 a mixturefof lnaphthalene land monochloracetic acid isheated to Vtemperature. of 165 to 185 C. and thus a condensation of the monochloracetic acid with the naphthalene Vis obtained with an escape of hydrochloric acid. But

one cansee'that the condensation described in the IU.-S. Patent 1,951,686 is successful only in very `rarecases; more particularly, it does not lead to the desired resgult when the starting materials whichare used are pure: the pure naphthalene -and the pure monochloracetic acid may be heated to the mentioned temperatures during practically unlimited periods of time without giving rise to 'the production of a substantial escape of hydrochloric acid and-without substantial formation of a-naphthylacetic acid.

'If a simple condensation of `a halogented alkyl on an aromatic nucleus with an escape of the corrspecttothe vhalogenated alkyl. Now, if such quantities of aluminium chloride or, possibly, iron chloride are added'to the reaction mixture and if said mixture is'heated'a substantial increase of vthe escape of4 hydrochloric acid isfound, but the Aformation .of :aenaphthylacetic acid is insignificant and tarry products are obtained which are insoluble in the alkalies.

It.was found that it is --possibld according to the method of the presentinventiontoexertV a favourable influence upon the :condensation of the naphthalene and of the' monochloracetic acid through/,an.additionofsmall quantities of the compounds of heavy metals `which in thezconditions of-the reaction are converted: into ...corresponding metallicchlorides. l\.'icstly,:the shape under which these metallic compounds are added to the'reaction-mixture is without any particular influence uponggthercourse of the reaction, but,

, generally, the: aqueous'solutions of the metallic salts give thebe'st'fyields; the organicsaltssuch as those of the acetic acid or of the monochloracetic acid come in secondlline whereas, for example, the .anhydrous metallic chlorides ;suc h as `"Ithose .whichare usedforithe-reaction offFriedel-l 2 Crafts :give the worstyields; cinenaphthylic acid.

`Asi-regardstheinetalliciion itselfit was formed by theapplicant that `a large number of-metals have -the property ofexerting amoreyorless-favourable `influence on the reaction of condensation between the naphthalene andlthegmonochleracetic acid. Asia characteristic property-these metals must only fulllthiscondition, as itsems to appear according to the observations l-c fthe applicant, that they form throughthefactionfof their chlorides on the-monochloraceticiacidin the conditions lof the reaction complex compounds whichare generallycharacterized in the course of the dissolution of the "metallic chlorides in-the monochloracetic acid' by vthe appearance -;of ya darker coloration in the `monochloracetic acid. It is known that metalliccompounds capable oi forming such complexes yare especially those of the metals which; inthe periodicalsystemof-the elements pertain to the groups of the vtransition elements with multiple rvvalences `andwith anfincomplete underla-yer; among these elements iron distinguishes itself Aby its-V tendency 'to Vsuch complexes. Now, according to,the-constatations1of the applicant theimetalsofthe abovementioned groups areprecisely those-which under the above indicated conditionspreferably actas catalystsin the method accordingto vthe invention and: among thesefmetalsgiron, more particularly, lends itself especially-well `togact asrascatalystfin the present reaction.

Apart from thegcharactper'of Athecatalyst-its concentration has l also 5 a @great importance for carrying*` outrthe :methodwaccording to `the invention. x-As it willbeffully indicated hereinafter for the example of irongthere existsfor every. metallic chloride a rather limited `concentration interval within-which the catalysts exerts'a favourable-influencexupon the formation of the a-naphthylacetic acid. When workingwithtoo low concentrations one will practically l:find :one-self in asituation which isv identical with thatg-of-the Working without anycatalyst such vas thatoffthe U.l S. Patent 1,951,686. ,On the contrary, :if the catalyst isused with a.; too high concentration the increase of 4,the quantityV of catalyst effectively determines aneacy celeration of the escape offhydrochloriciacid but instead of ai-naplit hylacetic acid ytarryproducts which are soluble only with diliculty or insoluble in most solvents are formed. Thus,` every metalis cncentrationilies approximately between @2150A Vtrichlorethylene or of similar bodies.

and -1 mole of compound of the active metal per mole of monochloracetic acid. For iron the optimum value is of the order of 10-3 mole of iron salt per mole of monochloracetic acid. A metal may generally be considered as a catalyst which is all the more active for carrying out the method which forms the subject-matter of the invention than the concentration of this metal corresponding to the maximum velocity of formation of the a-naphthylacetic acid is lower.

With the method in accordance with the invention it is, however, not only possible to fix an acetic rest on the naphthalene, but, if one works in the presence of a sui'licient excess of monochloacetic acid in the reaction mixture, it is also possible to make naphthyldiacetic acid. A mixture of a-naphthylacetic acid and naphthyldiacetic acid is then obtained; these products can readily be separated since, on the one hand, the boiling point of the naphthyldiacetic acid methyl ester is higher than that of the a-naphthylacetic methyl esterand, on the other hand, the naphthyldiacetic acid methyl ester is very diiiicultly soluble in cold alcohol in contradistinction with the a-naphthylacetic acid methyl ester which is very readily soluble even in cold alcohol, which also renders possible the separation of this latter through dissolution and re-crystallization.

Instead of naphthalene it is also possible to use similar hydrocarbons such as the benzene, the acenaphthene or the anthracene, this latter having, however, already a lower reactivity than ,thel naphthalene or the acenaphthene.

Instead of the monochloracetic acid itself it is possible, of course, also to resort to all those of its derivatives, which, in the conditions of the reaction, i. e. in heat and in the presence of water,V and hydrochloric acid, yield monochloracetic acid, for example: the anhydride of the monochloracetic acid or its mixed anhydrides or its esters.

For carrying out the method the necessary quantity of catalytically active metal, preferably as a chloride, a chloracetate or acetate in an aqueous solution is added to the monochloracetic acid, its anhydride or one of its esters. Instead of adding such an aqueous solution to the monochloracetic acid, it is also possible to mix a small quantity of water with the same and then to dissolve therein the metal or a metallic compound capable of being converted into a chloracetic under the action of the monochloracetic acid, for example the hydroxide or the carbonate. The monochloracetic acid and catalyst mixture is then heated while stirring during a certain time to 140-160" C. and the necessary quantity of hydrocarbon, naphthalene for example, is finally introduced. The temperature is then progressively raised to the boiling point of the monochloracetic acid and, simultaneously/the water contained in the vreaction mixture is separated by distillation. In order to facilitate the removal of the water by distillation it is advisable to form an azeotropic mixture by means of benzene, of

In measuring a-s the monochloracetic acid is consumed by the reaction the boiling point of the reaction mixture rises progressively so that when the heating is continued the temperature rises little by little in a corresponding manner in measuring as the reaction proceeds up to about G-210 C. As soon as the escape of hydrochloric acid ceases the hot mixture resulting from the reaction is poured while strongly stirring into an aqueous 'caustic' soda lye or into an aqueous suspension 75 4 of magnesia whereafter the mixture is still heated while stirring during a few hours and, finally, the insoluble parts are separated by filtration when cold. The filtrate is then acidied with hydrochloric acid; the precipitated a-naphthylacetic acid is expurgated of its liquid, washed with water and dried.

This application is a continuation-in-part of application S. N. 50,876, led September 23, 1948.

Example 1 Trivalent ironV monochloracetate was dissolved while heated and while stirring into 1.9 mole i. e. 185 grams 0f monochloracetic acid; after introduction of 3.75 moles i. e. 480 grams of naphthalene the reaction mixture was then heated to -185"v C. while stirring. The quantity of escaping hydrochloric acid was continuously checked; on the other hand, samples were taken regularly from the reaction mixture in order to follow the quantitative formation of a-naphthylacetic acid depending on the time. The appended Figure l is a graph comprising tWo curves c and b respectively showing the yields of a-naphthylacetic acid and HC1 obtained depending on the time for an iron concentration of 2 10n3 mole for 1.9 mole of monochloracetic acid.

The same test was effected in the presence of variable iron concentrations, all the other conditions remaining the same; for each iron concentration which was used the corresponding number of moles of a-naphthylacetic acid which was formed was plotted as an ordinate in the graph shown at Figure 2. Each curve represents the results which are obtained in the presence of variable iron concentrations for a different and well predetermined duration of the reaction. The curve which corresponds to the longest duration of the reaction gives the total yield in a-naphthylacetic acid formed for each selected iron concentration. Thus, the dotted line designated by l in Figure 2 which corresponds to an iron concentration of 2 103 reproduces the values obtained in the graph of Figure 1.

These curves show clearly that in the case of iron there is a net maximum of catalytic activity for a concentration of about 10-3 iron mole per mole of monochloracetic acid. If the iron concentration is reduced to about 10-4 mole the yield in a-naphthylacetic acid drops to a small fraction of the yield obtained with 10-3 mole of iron. In a similar manner, the yield in a-naphthylacetic acid is reduced in the measure as the iron concentration increases; for a concentration of 10-2 mole of iron this yield is about half that which is obtained with a concentration of 10-3 mole of iron.

Example 2 2 103 mole of anhydrous ferric chloride were dissolved while heated in 1.9 mole of monochloracetic acid. After introduction of 3.75 moles, i. e. 480 grams of naphthalene the reaction mixture was then heated to 18o-185 C. while stirring, as in Example 1. The escaping hydrochloric acid and the a-naphtylacetic acid which was formed were periodically measured; the measured quantities were plotted in the gram shown at Figure 3 in which the curves a and b respectively indicate the yields of a-naphthylacetic acid and in HC1 obtained depending on the time for a concentration of 2 103 mole of FeCls.

Example 3 VA mixture containing 37.6 grams of monochloracetic acid and 0.585 gram of an aqueous ysclutionof :ferrie zclrloridecontaimneiZiiglams.of iron per litre is prepared, which is thenzheated While stirring to G-1601.0..- during about 5 hours;

-51 grams of naphthalene are then introduced ftherein andithe'wholeis heatedto'190-195o C. In Y the course of this "heating the `watery-is removed fromthe reaction` mixture and in order to facilitate,thefdehydratiom'preferably 0:5 part by Weight ofbenzene or trichlorethyleneis added. E1n-'this i case the water 'is l removed by distillation in the form-of an Iazeotropic mixture; "the organic Asolvent riis preferably continuously returned vto `the reactionmixture As `soonas the `y temperature ofy thereaction mixturereachesabout 185'to 190 /Cr-a'strongiescapeof hydrochloricacid is initiated. "Inflthe measure yas the concentration between the monochloracetic acid and l thefnaphthalene proceeds and as the boiling point of the reaction mixture rises, simultaneously, in a corresponding @mannen fthe temperature is raised progressively ftd-20010121090; @After about 301 hours theescape fofhydrochlorio acid is terminated; the`- reaction myr-ni-xture f'vvhich. -vis still 'hot @is then pouredy while l1strongly"-fstirrin'g into :a'suspensionvof about 18 to 120 lpartsV of lmagnesia in from 500 to 800: parts -lofwaten 'Iheraqueous'` suspensionf is still heated 1While lstirring during one to twohours Yatxabout 80-90 .Then fthe mixture iszallovved` to decant;

ftheliquid .floating on thesurface ofl'the-slush "becomes'cleam it'isseparate'dl'through syphoning. 'The-'slush remaining in thetvesselsis.empasted with water and `then-.separated in A.a filter-press. The iiltrate is united with the deeanted liquid and this mixture is thenacidied While cold While `istirring,withhydrochloric acid. Thea-naphthyl- 1.acetic iacidi then-precipitates; in theashapei ofdine :needles exfvhich zare; almost '.white; itLis separated 'through zdehydration, .Washedwith water and v.driedunderr'vacuum .i'lhasoqobtained `yield is of "'40 partsl byweightiof ,arfnapht-hylacetic acid.

Example 4 '34'.5 grams` of= the `anhydride of the'monochloracetic -acid are miXed'With"0.-585 grarnfofY aeferric chloride' solution containing 24 grams of iron per litrey and`x then heated during 5 to'y 10 hours while stirring to 14C-160 `C.; 51 -parts bye-'Weight of naphthalene are then introduced andfthe operation is continued as iny Example 3; the elaboration ofthe .fa-.naphthlyaceticacid Which forms :also y.followsrthees.arr1e..process;v as.- in Example 3.

@ramble 5 idsgrams of-.imonochloracetic 1 acid ethyl ester are fmixe'dvwith '50.585 gramv of a "ferrie chloride f-solutionicontainingvZli gramsof iron perlitre and fwhileastirring; ilsparts by Weight -offnaphthalene :are then 2introduced"and "the operation is con- Atin-liedasin-Example 3; the elaboration of the .'.aenaphthylacetic :acid Which-'forms also follows ithetsamei process as in' Example 43.

EaxftfripZel 6 "A 'mixture vof 9415 grams of monoehloracetic acid and 0.5 gram of ferrie chloride is held at `165 .0. during 24 hours; 308 grams 4.ofniolten yacenaphthene .arethenj introduced and the mixture isheate'd to"1'80'C. during 48hours. Duringrthis periodrthe escape of hydrochloric acid isOJBmole.

Illhe reaction v.product is poured y on V.magnesia, crushedandground after cooling-and then yex- .,tracted withhoilinggwater. jTheli1tered solution yields `through .acidification 100.5 .grams of 15j acenaphtheneacetic--acid-.-having a. melting point of 181 C.

TEarzcmple37 Yacetic acid. vThe,mixture'ir/,as then heated-,to 18.0

C. and then such a quantitypf-.benzene Was added that .ay keen 'boiling occurred. i The. benzeneeseparated through distillation is condensed :inf-a cooler and continuously returned to .the lboiling mixture. The Asimultaneous Iescape ,of hydrovchloricacid yielded0.1031mole after 24 hours. I, For the separation of theyphenylaceticf,acid` from `the reactionl mixture the. major-part `of1then1ono chloracetic acid was rstfrmoved;throughgdis- .ti1lation, vthen .the residue; of v ,the.distillationywas treated when boiling with a suspensionotmagnesia in water. Then the Wholewasyjlteredsand the phenylacetic :acid was precipitatethrough acidiiication` of :the` solution. An aacid iwasfgobtained which was almost lWhite andxtheymelting point of whichis '75 C. `Withfa fyieldfgcorresponding to about 4% of thew quantityqothydrochloric acid which escaped.

1728 grams ofnaphthalene and'1275'lgramsof monochloracetic `acid are maintained' at V185" C. during`24 hours in the presencey of 40 grams of a ferricchloride solution containing24 gramsof iron per litre. Then 1275 grams of monochloracetic acid are added anew andthe temperature is raised progressivelyto 200 C. in'24 fhours. The total escape of hydrochloric acid is then 24.5

Y moles. The reaction `product is ydistilledin order to expel the monochloraceidc acid and the nonreacted naphthalene therefrom. Theresidueis treated With a suspension of magnesiaV in water; the solution is filtered While. coldand the'ltrate is precipitated'through hydrochloric acid. The mixture of the obtained acids (a-naphthylacetic acid-l-l-5 naphthylacetic acid) is esteried through methyl alcohol; Vtheesters are separated through fractioning under Vacuum.

The 1-5 naphthylacetate of `methyl issaponied through a solution of caustic soda and 'the 1:-5 naphthyldiacetic Vacid is then ,precipitated through hydrochloric acid; a white acidis obtained which melts at 315 C; whiledecomposing. The so obtainedyield is 510 grams of a-naphthylaceic acid and 327grams`of'1-5 naphthylacetic acl :Example 9 drochloric acid is ,1 8 grams. ,A distillation isthen effected the residue vof vv hic,h wasgtreated .2111.29.5- C. withl a. suspension ,of magnesiumxide in Water during 2'; hours While strongly stirring. After cooling the A.insoluble part .Was A.separated through filtration and the `alpha.naphthylacetic yacid was .precipitated in .the filtrate .through vacidification with hydrochloric acid. The -liltereid and A...dried .'alpha-naphthylacetic acid '.rep-

resents `.30grarrlsg its melting .pointis 1-28- $12920.,

Example 10 11.5 grams of manganese carbonate were heated While stirring with 180 grams of monochloracetic acid, the major part of the manganese carbonate thus being dissolved. After heating at about 160 C. during about 24 hours while strongly stirring, 480 grams of naphthalene were introduced and the mixture Was brought to a temperature of about 180 C. during 100 hours. During this operation 13 grams of hydrochloric acid escaped. The non-converted starting materials were then distilled under a normal pressure; the residue of the distillation was poured onto finely powdered hydrated magnesia and the whole was well mixed.

After cooling the mass was ground and extracted with Water.

After filtration of the insoluble part the anaphthylacetic acid Was precipitated in the filtrate through hydrochloric acid and then expurgated of its liquid and dried. The obtained alpha-naphthylacetic acid is snow White and has a melting point of 12H-128 C.

Example 11 11 grams of nickel carbonate were dissolved While stirring in 180 grams of monochloracetic acid. After a heating of about 24 hours at about 160 C. While strongly stirring, 480 grams of naphthalene Were introduced and the mixture was brought While stirring Well to l80l83 C. during 100 hours, 14 grams of hydrochloric acid escaping during this operation. The non-converted starting materials were then distilled under a normal pressure; the residue of the distillation was poured onto finely ground slacked lime and the whole was mixed well. The so obtained mass Was then treated as in Example l, which yielded 10 grams of alpha-naphthylacetic acid the melting point of which is 12S-129 C.

Example ,Z2

13.9 grams of chromium hydroxide were dissolved While stirring and heating in 180 grains of monochloracetic acid. After heating at about 160 C. during about 24 hours while strongly stirring, 480 grams of naphthalene were introduced and the mixture was brought to 180185 C. during 100 hours. 33 grams of hydrochloric acid escaped during this operation; the residue of the distillation was then treated at 95-100 C. with a suspension of magnesia in Water during 2 hours While stirring strongly. After cooling the insoluble part Was separated through filtration and the alpha-naphthylacetic acid was precipitated in the filtrate through acidification with hydrochloric acid. The obtained alpha-naphthylacetic acid has a melting point of 127-l28 C. The formation of secondary tarry products Was particularly small in this case.

Example 13 1.8 grams of powdered cobalt (80 mesh) were dissolved in 180 grams of monochloracetic acid. After a heating of about 24 hours at about 160o C. while strongly stirring at about 160 C. 480 grams of naphthalene were added and the mixture was brought to 185-195 C. while stirring. After a heating of 96 hours the quantity of hydrochloric acid which had escaped was of 19 grams. The whole was then distilled and the residue of the distillation was treated as indicated in Example l2. After precipitation of the acid, filtration and drying and a-naphthylacetic 8 acid was obtained the melting point of which is 128r C.

Example 14 1 gram of titanium tetrachloride was dissolved in 285 grams of monochloracetic acid. After heating at C. during about 24 hours while strongly stirring 576 grams of naphthalene were introduced and the mixture was brought to 18S-190 C. After a heating of 48 hours the quantity of hydrochloric acid Which had escaped was 26 grams. The whole was then distilled and the residue of the distillation Was treated as indicated in Example 13. After precipitation of the acid, filtration and drying, an a-naphthylacetic acid was obtained the melting point of which is 128 C.

Example 15 1 gram of zirconium chloride in an aqueous hydrochloric acid solution was introduced into 285 grams of monochloracetic acid. After a heating of 50 hours at 165 C. 384 grams of naphthalene Were introduced and the mixture was brought to IS7-191 C After a heating of 94 hours the quantity of hydrochloric acid which escaped Was 81 grams. The whole was then distilled and the residue of the distillation was treated as indicated in Example 12. After precipitation of the acid, filtration and drying, an alpha-naphthylacetic acid was obtained the melting point of which was 12B-129 C'.

Example 16 0.05 mole of cerium is dissolved in 1 mole of monochloracetic acid. 1.9 mole of naphthalene are then added and the mixture is heated to C. After 10 hours the hydrochloric acid Which had escaped was 0.53 mole. The major part of the monochloracetic acid and of the naphthalene was removed from the reaction mixture and extracted by distillation; the residue of the distillation was then treated While heating and stirring through an aqueous suspension of magnesia. After filtration the la-naphthylacetic acid which had formed was separated from the filtrate through precipitation by means of hydrochloric acid.

Example 17 0.530 gram of platinum tetrachloride and 2 grams of Water were introduced into 236 grams of molten monochloracetic acid; the mixture was then heated to 160 C. during 30 hours. 320 grams of naphthalene were then added and the temperature of the reaction mixture was brought to about C. After a reacting of 40 hours the total quantity of hydrochloric acid which had escaped reached 0.24 mole. The major part of the monochloracetic acid and of the naphthalene was extracted through distillation; the residue of the distillation was then treated while heating and stirring through an aqueous suspension of magnesia. After filtration the a-naphthylacetic acid which had formed was separated from the filtrate through precipitation by means of hydrochloric acid.

We claim:

1. A method for the manufacture of arylacetic acids by condensing one of the hydrocarbons of the group consisting of naphthalene, benzene, acenaphthene, and anthracene With one 0f the chlorinated compounds of the group consisting of monochloracetic acid, esters, anhydride and mixed anhydrides of said acid, Which comprises heating for several hours at high temperature while stirring said hydrocarbon with said chlorinated compounds inthe presence of an iron catalyst in an amount between 10*4 to 2X1()-3 inoles per mole of alkyl-ating agent.

2. A method for the manufacture of arylacetic acids by condensing one of the hydrocarbons of the group consisting of naphthalene, benzene, acenaphthene and anthracene With one of the chlorinated compounds of the group consisting of monochloracetic acid, esters, anhydrides and mixed anhydrides of said acid, which comprises heating for several hours at high temperature While stirring said hydrocarbon with said chlorinated compound in the presence of a catalyst selected from the group consisting of iron, manganese, nickel, chromium, cobalt, titanium, zirconium, cerium and platinum, in an amount between 104 and about 7x103 moles per mole of alkylating agent.

3. A method for the manufacture of naphthylacetic acid by condensing naphthalene with one of the chlorinated compounds of the group consisting of monochloracetic acid, esters, an-

hydrides and mixed anhydrides of said acid,

which comprises heating for several hours at high temperature while stirring said hydrocarbon with said chlorinated compound in the presence of an iron catalyst in an amount between 10-4 and 2 103 moles per mole of alkylating agent.

4. A method for the manufacture of naphthylacetic acid by condensing naphthalene with one of the chlorinated compounds of the group consisting of monochloracetic acid, esters, anhydrides and mixed anhydrides of said acid, which comprises heating for several hours at high temperature While stirring said hydrocarbon with said chlorinated compound inthe presence of a catalyst selected from the group consisting of iron, manganese, nickel, chromium, cobalt, titanium, zirconium, cerium and platinum, in an amount between 10-4 and about 7x10-2 moles per mole of alkylating agent.

5. A method for the manufacture of arylacetic acids by condensing one of the hydrocarbons of the group consisting of naphthalene, benzene, acenaphthene, and anthracene with one of the chlorinated compounds of the group consisting of monochloracetic acid, esters, anhydrides and mixed anhydrides of said acid, which comprises heating for several hours at high temperature while stirring said hydrocarbon with said chlo rinated compound in the presence of a manganese catalyst in an amount on the order of about 5 1-2 moles per mole of alkylating agent.

6. A method for the manufacture of arylacetic acids by condensing one of the hydrocarbons of the group consisting of naphthalene, benzene, acenaphthene, and anthracene with one of the chlorinated compounds of the group consisting of monochloracetic acid, esters, anhydrides and mixed anhydrides of said acid, which comprises heating for several hours at high temperature While stirring said hydrocarbon with said chlorinated compound in the presence of a nickel catalyst in an amount on the order of about 5x10-2 moles per mole of alkylating agent.

'7. A method for the manufacture of arylacetic acids by condensing one of the hydracarbons of the group consisting of naphthalene, benzene, acenaphthene, and anthracene with one of the chlorinated compounds of the group consisting of monochloracetic acid, esters, anhydrides and mixed anhydrides of said acid, which comprises heating for several hours at high temperature while stirring said hydrocarbon with said chlorinated compound in the presence of a chromium catalyst in an amount on the order of about '1x10-2 moles per mole of alkylating agent.

8. A method for the manufacture of arylacetic acids by condensing one of the hydrocarbons of the group consisting of naphthalene, benzene, acenaphthene, and anthracene with one of the chlorinated compounds of the group consisting of monochloracetic acid, esters, anhydrides and mixed anhydrides of said acid, which comprises heating for several hours at high temperature while stirring said hydrocarbon with said chlorinated compound in the presence of a cobalt catalyst in an amount on the order of about 2 l0*2 moles per mole of alkylating agent.

RENE' LON LEHMANN. JOSEF LINTNER.

REFERENCES CITED The following references are of record in the file of this patent:

Adams et al., Organic Reactions, (Wiley): Vol. III, pages 2, 3, 21-55, (1946) 

2. A METHOD FOR THE MANUFACTURE OF ARYLACETIC ACIDS BY CONDENSING ONE OF THE HYDROCARBONS OF THE GROUP CONSISTING OF NAPHTHALENE, BENZENE, ACENAPHTHENE AND ANTHRACENE WITH ONE OF THE CHLORINATED COMPOUNDS OF THE GROUP CONSISTING OF MONOCHLORACETIC ACID, ESTERS, ANHYDRIDES AND MIXED ANHYDRIDES OF SAID ACID, WHICH COMPRISES HEATING FOR SEVERAL HOURS AT HIGH TEMPERATURE WHILE STIRRING SAID HYDROCARBON WITH SAID CHLORINATED COMPOUND IN THE PRESENCE OF A CATALYST SELECTED FROM THE GROUP CONSISTING OF IRON, MANGANESE, NICKEL, CHROMIUM, COBALT, TITANIUM, ZIRCONIUM, CERIUM AND PLATINUM, IN AN AMOUNT BETWEEN 10-4 AND ABOUT 7X10-3 MOLES PER MOLE OF ALKYLATING AGENT. 